CN103665232A - Method and apparatus for preparing polymer beads of uniform particle size by suspension polymerisation - Google Patents
Method and apparatus for preparing polymer beads of uniform particle size by suspension polymerisation Download PDFInfo
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- CN103665232A CN103665232A CN201310426072.8A CN201310426072A CN103665232A CN 103665232 A CN103665232 A CN 103665232A CN 201310426072 A CN201310426072 A CN 201310426072A CN 103665232 A CN103665232 A CN 103665232A
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- B01F35/71—Feed mechanisms
- B01F35/717—Feed mechanisms characterised by the means for feeding the components to the mixer
- B01F35/71755—Feed mechanisms characterised by the means for feeding the components to the mixer using means for feeding components in a pulsating or intermittent manner
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- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
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- C08F2/00—Processes of polymerisation
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- B01J2219/00049—Controlling or regulating processes
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- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00094—Jackets
Abstract
The invention relates to method and apparatus for preparing polymer beads of uniform particle size by suspension polymerization. Monomer solution and liquid solution immiscible with the monomers in the monomer solution are cocurrently jetted upwardly in a pulsating manner in a reaction vessel. Monomer droplets are allowed to rise up in a controlled and smooth manner under the dynamic forces exerted by differential flow rate and differential pressure between the monomer and liquid solutions and the differential densities between the monomer and liquid solutions without causing coalescence, agglomeration and breakup of the monomer droplets and to stabilize by partial polymerization of the droplets at 50-60 DEG C. The monomer droplets flow out horizontally into a polymerization reactor and get polymerized in the polymerization reactor under agitation at 80-85 DEG C. The polymer beads are dried at 80-100 DEG C. and sieved. The invention is easy for realization, the energy requirement is lowered, the cycling period is shortend, and the cost effectiveness is ensured.
Description
Technical field
The present invention relates to prepare by suspension polymerization the method and apparatus of the polymer beads of homogeneous particle diameter.
Background technology
By suspension polymerization, preparing the method for the polymer beads of homogeneous particle diameter (UPS) carries out conventionally in the following manner: by pore, the organic phase of the polymerization single polymerization monomer that contains initiator is sprayed in the unmixability liquid phase that contains suspension stabilizer, to form monomer droplet in this liquid phase, then will make monomer droplet aggregate into polymer beads.Conventionally polymer beads is converted into various ion exchange resin.Zeo-karb makes by sulfonated polymer bead, and chloromethylation and amination polymer beads will provide anionite-exchange resin.In the situation of vinylformic acid Zeo-karb, after acroleic acid polymerization, carry out follow-up hydrolysis and the ammonia solution of acrylic anionic exchange resin.Ion exchange resin has widespread use, for example, can be used for the decolouring of the removing of various water treatment applications, deoxidation or dealkalize application, pollutent or impurity, sugar or water, or the recovery of metal.
Koestler and Robin (US3922255) have described a kind of method of preparing the polymer beads of homogeneous particle diameter by suspension polymerization, described method comprises: make monomer liquid from one end of the first post (drop formation post), enter the first post by the foraminate perforated disc of tool, monomer unmixability waterborne liquid is entered in the same way from the described end of the first post, make the liquid that contains drop enter the top of the second post (gel column) and the aqueous flow flowing downward is introduced to the top of the second post in the same way so that described drop is partially polymerized from the other end of the first post, making to be dispersed in partially polymerized drop in waterborne liquid is flowed in separation vessel so that drop gravity separation by the bottom of the second post, and the drop in concentrated waterborne liquid, and make the drop slurry relatively concentrating by separation vessel, be flowed to the storage tank that stirs polymerization reactor, wherein drop is further polymerized to polymer beads.
Aforesaid method need to be used to form and a large amount of devices of concentrated drop, drop form post, for the gel column of partially polymerized and stable droplet, with for concentrated drop with form the separation vessel of drop slurry.Because needs install in a large number, therefore very high for implementing the cost of device configuration of the method.Because monomer, aqueous solution and drop pass through a series of devices in complicated zigzag mode, the cycle time of therefore implementing the method is also longer.In addition, monomer phase and water-based form the bottom of post and sidepiece by drop respectively mutually and enter drop and form post, and in gel column, the liquid that contains drop is entered by its sidepiece, and aqueous flow is entered by its top.As a result, at drop, form in post and gel column and exist and hinder droplet flow and coalescent possibility, can affect thus the homogeneity of drop, and finally can affect the homogeneity of polymer beads.
Lange and Striiver (US4427794) have described a kind of manufacture method having through the homogeneous particle diameter of improvement and the polymer beads of homogeneous quality, and described method comprises: use concentric double nozzle to be supplied in reaction column in the same way by monomer solution with the bottom of the immiscible aqueous solution of monomer solution by reaction column.Described post comprises drop forming section, seals part and shell sclerosis part.In the drop forming section of reaction column, in aqueous solution, form the drop of monomer.By being supplied in the corresponding section of reaction column sealing with the sidepiece of shell hardener by reaction column, drop by reaction column seal with shell sclerosis part in seal respectively and harden.The temperature of the different piece of reaction column is different, and by monitoring device, is controlled independently.Make to flow downward and enter in aggregation container by reaction column through the drop of sealing and shell hardens.Owing to being sealed, in the whipping process of drop in aggregation container, will be stable, drop is in being wherein further polymerized to polymer beads.After polymerization, remove encapsulation object.
In aforesaid method, monomer droplet forms, seals and shell sclerosis in the different piece of same reaction column, and the differing temps of reaction column various piece is controlled by monitoring device independently.In addition, the method relates to removing of drop shell.Due to all of these factors taken together, will extend cycle time, and the enforcement of the method is very expensive, difficulty and loaded down with trivial details.Device for monitoring temperature can increase fund and the maintenance cost of reaction column and reduce reliability.Due to the thermograde between reaction column various piece, drop may experience thermal shocking.Also exist because hindering droplet flow and coalescent possibility from sealing with flowing of shell hardener of reaction column sidepiece.The thermal shocking of drop and the coalescent homogeneity that will reduce polymer beads.
Timm (US4444961) has instructed the method and apparatus of preparing homogeneous particle diameter polymer beads.By the monomer that makes to comprise polymerizable monomer, by thering is the orifice plate of a plurality of apertures, flow into the continuous suspending phase comprising with the immiscible liquid of described monomer and stablizer, form the monomer jet with laminar flow characteristics.The vibrated excitation of monomer jet, take and spued as comprising the drop of monomer.Drop is polymerized to sphere polymers bead in aggregation container.
Vibrational excitation is by offering monomer jet as vibrating devices such as machinery, electroacoustic, the underwater sound or electromagnetic vibrator or magnetic resistance transverters, and all these devices have all improved cost with regard to fund input, maintenance and energy consumption, and have also reduced reliability.Due to vibrational excitation, thereby also exist droplet coalescence to reduce the possibility of the size distribution homogeneity of polymer beads.In addition, described liquid phase is by the sidepiece access arrangement of equipment, and the orifice plate of described monomer phase jet by device bottom enters liquid phase in the upward direction.Also due to this point, there is the possibility that hinders the mobile and coalescent of drop and then reduce the size distribution homogeneity of polymer beads.
Miyata etc. have described a kind of method of preparing oil-in-water-type homogeneous dispersion of droplets.The method comprises to be injected oil type monomer in the aqueous medium that contains dispersion stabilizer, the nozzle plate that forms external phase and can upwards spray a plurality of perforation of hydrophobic liquid by having makes proportion move up lower than the hydrophobic liquid of this aqueous medium, to form the drop of hydrophobic liquid in aqueous medium.Nozzle plate comprise around do not arrange perforation centre portions circular array for spraying a large amount of perforation of hydrophobic liquid,, this perforation is not evenly set on whole surface, can effectively form excellent dispersion thus and not make near the hydrophobicity liquid stream spraying with penetrating perforation shake, and a large amount of perforation for injection is provided on the whole, and improves the productive rate of dispersion.
In the situation of method that relates to the polymer beads of preparing homogeneous particle diameter, hydrophobic liquid is the polymerizable monomer that contains polymerization starter.The equipment that the entrance that the dispersion of the polymerizable monomer of droplet size homogeneous is arranged in top and monomer and aqueous medium in outlet is positioned at bottom forms.Dispersion is discharged continuously by the top outlet of this equipment, and introduces in polymerization reactor to aggregate into the polymer beads of homogeneous size.The aqueous medium that contains dispersion stabilizer is supplied to equipment continuously by the sidepiece of equipment, to form the dispersion of the monomer of droplet size homogeneous, this dispersion use Filled Dielectrics, thus the external phase that moves up and exported the aqueous medium of discharging continuously by the top of equipment formed.The front end of the monomer entrance of equipment bottom is provided with for forming mutually the nozzle plate of monomer droplet with water-based.
In the document of Miyata etc., monomer solution and aqueous solution are oppositely supplied with, thereby have the possibility that monomer droplet is coalescent and hinder the drop in aqueous solution to move up, and have reduced thus the homogeneity of polymer beads size distribution.In addition, need to apply larger power to impel the monomer droplet in aqueous solution to move up to jet, thereby improve the power requirement of equipment.
EP2088161A1 has described a kind of method of preparing the crosslinked bead polymers of single decentralized, described method comprises: by harmonic mean particle diameter (harmonic mean size), be that the aperture that 50 microns～1500 microns and the drop that comprises at least one monomer, at least one linking agent and radical polymerization initiator form in container by drop is introduced in aqueous medium, take and manufacture the waterborne suspension of not sealing drop that the volume fraction of drop is 35%～64%.The waterborne suspension of drop is flowed in a downward direction in pipeline, making the harmonic mean particle diameter of drop and the ratio of internal diameter of the pipeline is 0.001～0.35, average line flow velocity is 0.5ft/s～2.5ft/s (0.15m/s～0.75m/s), and temperature was remained on than the transformation period of polymerization starter is that the temperature of 1 hour is low at least 20 ℃.Monomer droplet polymerization in the polymerization reactor that is arranged on lower position (level) with respect to drop formation container.
Monomer droplet sprays by involving vibrations and is naturally injected in interior currently known methods and forms.It is very difficult that polymer liquid is dripped the flow control entering under gravity in polymerization reactor, has the possibility of droplet coalescence and obstruction droplet flow, thereby affects the homogeneity of the size distribution of polymer beads.Other vibration jet mechanism will increase cost and reduce reliability aspect fund input, maintenance and energy consumption.
Therefore, still to prepare the method and apparatus of the polymer beads of homogeneous particle diameter by suspension polymerization, there is demand, described method and apparatus should be able to be simply and is easily implemented, and has cost benefit and so that homogeneous particle diameter and the improved polymer beads of quality to be provided shorter cycle time.
Summary of the invention
According to the present invention, a kind of method of preparing the polymer beads of homogeneous particle diameter by suspension polymerization is provided, described method comprises:
(i) at flow velocity and the 0.2Kg/cm of 2 ls/h～4 ls/h
2～1Kg/cm
2pressure under, with pulse mode, by being positioned at the monomer droplet of vertical setting, form a plurality of 50 microns～300 microns big or small apertures with reaction container bottom, the monomer solution of the polymerization single polymerization monomer that contains initiator is injected into the monomer liquid drip that makes progress mobile, and the while is at flow velocity and the 2.5Kg/cm of 4 ls/h～8 ls/h
2～3Kg/cm
2pressure under, with pulse mode by the hole of the periphery around described aperture and a plurality of 0.5mm～1mm sizes that are positioned at reaction container bottom that separate above aperture, to be injected in the same way the mobile fluid that makes progress with monomer unmixing and the liquor that contains suspension stabilizer, volume ratio between described monomer solution and liquor is 1:10, and described hole separates above described aperture with the distance of 10mm～40mm;
(ii) under the power applying at the density difference between the current difference between the pulsating supply source of monomer solution and liquor and pressure reduction and monomer solution and liquor, make monomer droplet in described liquor with controlled and stably mode in reaction vessel, rise, and do not cause coalescent, the aggegation of monomer droplet and break, and in reaction vessel at 50 ℃～60 ℃, by the suspension stabilizer in liquor, by the partially polymerized monomer droplet stabilization that makes of drop;
(iii) make the monomer droplet in liquor flatly flow into polymerization reactor from reaction vessel, and carrying out polymerization in 80 ℃～85 ℃ in described polymerization reactor, described polymerization reactor is equipped with agitator and is positioned at the position higher than reaction vessel;
(iv) at 80 ℃～100 ℃ dry polymer beads; With
(v) sieving polymer bead.
According to the present invention, a kind of equipment of preparing the polymer beads of homogeneous particle diameter by suspension polymerization is also provided, described equipment comprises: the monomer droplet formation reaction vessel vertically arranging, it limits the monomer solution dispenser that is positioned at reaction container bottom continuously, be positioned at monomer droplet observation first hyalomere of monomer solution dispenser top, be positioned at the monomer droplet stabilization portion of the first hyalomere top, the monomer droplet that is positioned at monomer droplet stabilization portion top is observed with the second hyalomere and is positioned at the second hyalomere top and is positioned at turbulent flow inhibition and the drop discharge portion at reaction vessel top, wherein, monomer solution dispenser is connected with pulsating monomer solution supply source in its bottom, described monomer solution supply source can be at flow velocity and the 0.2Kg/cm of 2 ls/h～4 ls/h
2～1Kg/cm
2pressure under with pulse mode, supply with the monomer solution contain initiator, and monomer solution dispenser comprises the injection orifice plate with a plurality of 50 microns～300 microns of big or small apertures at its top, the first hyalomere comprises the injection hollow tubular ring that is positioned at its bottom and separates with distance and the described orifice plate of 10mm～40mm with respect to described orifice plate above described orifice plate, described tubular ring around the aperture periphery in described orifice plate and thereon surface there is the hole of a plurality of 0.5mm～1mm sizes that separate, described tubular ring is connected with pulsating liquor supply source, described liquor supply source can be with flow velocity and the 2.5Kg/cm of 4 ls/h～8 ls/h
2～3Kg/cm
2pressure feed and monomer solution unmixing the liquor that contains suspension stabilizer, volume ratio between described monomer solution and described liquor is 1:10, and monomer droplet stabilization portion comprises heating unit, partly the monomer droplet in liquor is heated and stabilization in 50 ℃～60 ℃ in described monomer droplet stabilization portion, and turbulent flow suppresses to comprise with drop discharge portion the monomer droplet outlet pipe being connected with polymerization reactor with horizontal droplet flow pipe, described polymer reactor is positioned near the position higher than reaction vessel horizontal droplet flow pipe, and its top is connected with described horizontal droplet flow pipe, described polymerization reactor is equipped with agitator and heating unit to heat and to make monomer droplet aggregate into polymer beads at 80 ℃～85 ℃, described polymerization reactor also has in its bottom the polymer beads delivery pipe that has been equipped with valve.
The operable monomer solution that contains initiator of the present invention with the example of the liquor that contains suspension stabilizer is: the monomer solution that comprises vinylbenzene, Vinylstyrene (DVB) and benzoyl peroxide (BPO) and the liquor that comprises water, polyvinyl alcohol and NaCl, obtain gel type polystyrene-DVB multipolymer; The monomer solution that comprises vinylbenzene, Vinylstyrene, isopropylcarbinol (IBA) and benzoyl peroxide and the liquor that comprises water, hydroxy ethyl cellulose (HEC), calcium chloride, sodium lignosulfonate and NaCl, obtain macropore (MP) type polystyrene-DVB multipolymer; The monomer solution that comprises vinylbenzene, benzoyl peroxide and Vinylstyrene and comprise water, polyvinyl alcohol, NH
4the liquor of Cl, maxfloc T (poly-DMDAAC) and SLS (sodium laurylsulfonate), obtains detailed catalogue type polystyrene-DVB multipolymer; Comprise Vinylstyrene, benzoyl peroxide, as the monomer solution of toluene or heptane equal solvent and the liquor that comprises water, HEC, SLS and calcium chloride, obtain adsorptive type polystyrene-DVB multipolymer; Comprise ethyl propenoate, methyl methacrylate (MMA), Vinylstyrene, azobis isobutyronitrile and as the monomer solution of the hydrophobic solvents such as heptane and the liquor that comprises water, HEC and calcium chloride, obtain polyacrylic acid-DVB type multipolymer; The monomer solution that comprises methyl acrylate, Vinylstyrene, IBA and benzoyl peroxide and the liquor that comprises water, NaCl, calcium chloride, HEC, obtain MP type polyacrylic acid-DVB multipolymer; The monomer solution that comprises ethyl propenoate, methacrylic acid, Vinylstyrene, azobis isobutyronitrile and the liquor that comprises water, HEC and calcium chloride, obtain negatively charged ion gel-type polyacrylic acid-DVB multipolymer; The monomer solution that comprises ethyl propenoate or methyl acrylate, methacrylic acid, Vinylstyrene and azobis isobutyronitrile and the liquor that comprises water, carboxymethyl cellulose (CMC) and sodium-chlor, obtain gel-type acrylic copolymer; Or the monomer solution that comprises ethyl propenoate, methacrylic acid, Vinylstyrene, heptane, azobis isobutyronitrile and the liquor that comprises water, CMC and sodium-chlor, obtain MP type acrylic copolymer.
Accompanying drawing explanation
In accompanying drawing:
Fig. 1 be an embodiment of the invention by suspension polymerization, prepare the schematic diagram of equipment of the polymer beads of homogeneous particle diameter;
Fig. 2 is the bottom enlarged diagram of the equipment of Fig. 1; With
Fig. 3 is the orifice plate of equipment and the schematic top view of tubular ring of Fig. 1.
Embodiment
As shown in Fig. 1～3 of accompanying drawing, the equipment 1 of preparing the polymer beads of homogeneous particle diameter by suspension polymerization comprises that the monomer droplet of vertical setting forms reaction vessel 2, and it defines continuously and is positioned at the monomer solution dispenser 3 of reaction container bottom, the monomer droplet that is positioned at monomer solution dispenser top and observes with the first hyalomere 4, the monomer droplet stabilization portion 5 that is positioned at the first hyalomere top, the monomer droplet that is positioned at monomer droplet stabilization portion top and observe with the second hyalomere 6 and be positioned at above the second hyalomere and be positioned at turbulent flow inhibition and the drop discharge portion 7 of container top.
Monomer solution dispenser 3 is spherical form, and comprises top mounting flange 8 and the monomer solution aspiration channel 11 that is provided with the monomer solution tail pipe 9 of inlet valve 10 and is provided with ventilation valve 12.Monomer solution dispenser sucks the process of monomer solution and carries out in the following manner: open inlet valve 10 and breather valve 12, and make monomer solution flow through monomer solution dispenser.Monomer solution dispenser is connected with the pulsating monomer solution supply source of the monomer solution that can contain initiator with pulse mode supply in its bottom.As an example, pulsating monomer solution supply source comprises tank 13, and tank 13 has monomer solution and is connected with the bottom of monomer solution dispenser by peristaltic pump 14, spinner-type flowmeter 15 and pressure warning unit 16.Monomer solution dispenser 3 comprises orifice plate 17 at its top, and orifice plate 17 has a plurality of 50 microns～300 microns big or small apertures 18 (Fig. 2 and 3).Monomer solution dispenser and orifice plate are preferably made by stainless steel.Monomer solution dispenser contributes to prevent turbulent flow, and contributes to schedule of apportionment liquid solution equably to pass orifice plate.
Monomer droplet is observed and preferably by tempering transparent glass, is made with the first hyalomere 4, and comprises bottom mounting flange 19 and top mounting flange 20, and bottom mounting flange 19 is removably fixed on the top mounting flange 8 of monomer solution dispenser.The first hyalomere 4 also comprises and is positioned at its bottom and above orifice plate and the hollow tubular ring 21 being spaced from (Fig. 2 and 3).Tubular ring is around the periphery of the aperture in orifice plate, and its upper surface has the hole 22 of a plurality of 0.5mm～1mm sizes that separate.Tubular ring is preferably made by stainless steel, and is connected with pulsating liquor supply source, and described liquor supply source can be supplied with and monomer solution unmixing the liquor that contains suspension stabilizer.As an example, pulsating liquor supply source comprises tank 23, and tank 23 has liquor and is connected with tubular ring by peristaltic pump 24, spinner-type flowmeter 25 and pressure warning unit 26.
Monomer droplet stabilization portion 5 is preferably made by stainless steel, and comprising the lining 27 with hot-fluid entrance 28 and hot-fluid outlet 29, this lining 27 is for cycling through hot-fluid (not shown) and adding the monomer droplet of thermostabilization portion with the 50 ℃～temperature of 60 ℃.Lining 27 is preferably made by soft steel.Monomer droplet stabilization portion comprises the bottom mounting flange 30 of its bottom and the top mounting flange 31 at its top, and bottom mounting flange 30 is removably fixed on the top mounting flange 20 of the first hyalomere.
The second hyalomere 6 is preferably made by tempering transparent glass, and comprises the bottom mounting flange 32 of its bottom and the top mounting flange 33 at its top, and bottom mounting flange 32 is removably fixed on the top mounting flange 31 at monomer stabilization portion top.The turbulent flow inhibition at reaction vessel top and drop discharge portion 7 are preferably spherical, and comprise the bottom mounting flange 34 of its bottom, and it is removably fixed on the top mounting flange 33 of the second hyalomere.Turbulent flow inhibition and drop discharge portion also comprise the drop outlet pipe 35 at its top, and drop outlet pipe 35 is provided with liquor and inhales valve 36 and be connected with the horizontal droplet flow pipe 37 that is provided with valve 38.Reference numeral 39 represents the bypass pipe that is provided with valve 40 and is connected with drop outlet pipe.Turbulent flow suppresses and drop discharge portion contributes to suppress the turbulent flow of monomer droplet in liquor, and guarantees that the monomer droplet in liquor steadily flows out from reaction vessel.Reaction vessel is inhaled valve 36 and inhalant liquid liquid solution by opening.In the situation of the monomer droplet by-pass flow that for example need to make for the object of test to flow out by drop outlet pipe, by opening valve 40, open bypass pipe, and with bypass pipe, collect the sample of monomer droplet by test.
This equipment is positioned at the polymerization reactor 41 higher than the position of reaction vessel near being also included in horizontal droplet flow pipe, and polymerization reactor 41 is equipped with agitator 42 and lining 43, hot-fluid entrance 44 and flow of heated fluid that lining 43 is provided with for making hot fluid circulation pass through lining export 45, so that keep the polymerization temperature of 80 ℃～85 ℃ in polymerization reactor.Polymerization reactor is also provided with the polymer beads delivery pipe 46 with valve 47.The agitator motor of polymerization reactor is labeled as to 48.
For prepare the polymer beads of homogeneous particle diameter by suspension polymerization, at flow velocity and the 0.2Kg/cm of 2 ls/h～4 ls/h
2～1Kg/cm
2pressure under, preferably at flow velocity and the 0.3Kg/cm of 2.7 ls/h～3.3 ls/h
2～0.5Kg/cm
2pressure under, with pulse mode, by the aperture 18 in the orifice plate 17 of reaction vessel 1 bottom, the monomer solution (not shown) of the polymerization single polymerization monomer that contains initiator is injected into the monomer liquid drip (not shown) that makes progress mobile.Meanwhile, at flow velocity and the 2.5Kg/cm of 4 ls/h～8 ls/h
2～3Kg/cm
2pressure under, preferably at flow velocity and the 2.8Kg/cm of 5 ls/h～6 ls/h
2pressure under, the hole 22 of the upper surface by the tubular ring 21 that separates above orifice plate, will be injected into the mobile fluid that makes progress in the same way with monomer unmixing and the liquor (not shown) that contains suspension stabilizer.Volume ratio between monomer solution and liquor is 1:10, is preferably 1:4.Hole on tubular ring is arranged on the top of aperture in orifice plate with the distance of 10mm～40mm, preferred 25mm.By the first hyalomere 4, observing monomer droplet forms.
The monomer solution spraying in difference of altitude by with 10mm～40mm and the fluctuating velocity between liquor is poor and pressure reduction and monomer solution and liquor between the power applying in the upward direction that causes of density difference under, monomer droplet in liquor with controlled and stably mode in reaction vessel 1, move up, and do not cause coalescent, the aggegation of drop and break.By making, if the hot fluid circulations such as hot water are by the lining in drop stabilization portion, the temperature in the drop stabilization portion 5 of reaction vessel to be remained to 50 ℃～60 ℃.Due in liquor as the existence of the stablizers such as polyvinyl alcohol (PVA), monomer droplet will, 50 ℃～60 ℃ partly polymerization stabilizations, upwards flow simultaneously in drop stabilization portion.
By the second hyalomere 6, observe the stabilized monomer drop that makes progress mobile.Stabilized monomer drop is flowed out through outlet pipe 35 by the top of reaction vessel 1, then through horizontal flow pipe 37, flatly flows in polymerization reactor 41.At 80 ℃～85 ℃, by agitator 42, stir, make drop polymerization in polymerization reactor 41.By opening the valve 47 in delivery pipe, through delivery pipe 46 from polymerization reactor collected polymer bead.80 ℃～100 ℃, preferably at 90 ℃, preferably in pan dryer dry polymer bead and screening.
According to the present invention, by spraying monomer solution with pulsating current difference and pressure reduction and at a certain distance by monomer solution top atomizing of liquids solution in the same way, monomer droplet is by generation, stabilization and up carry in liquor.Make the drop in liquor increase in reaction vessel with steady and controlled intermittent mode, partly polymerization, utilizes the stablizer being present in liquor under the controlled temperature of 50 ℃～60 ℃ to carry out stabilization, and flows out reaction vessel.Because the monomer droplet in liquor steadily upwards flows, so the coalescent and aggegation of drop and breaking is prevented.Drop also can not stand any thermal shocking, because only keep a temperature in the drop stabilization portion of reaction vessel.Because monomer droplet flatly flows in horizontal flow pipe 37, therefore when flowing into polymerization reactor by reaction vessel, the aggegation of monomer droplet and breaking is also prevented.Because monomer droplet has carried out stabilization, so they can aggegation in polymerization reactor or be damaged.
The present invention has abandoned sealing with the shell that removes of shell sclerosis and monomer droplet of monomer droplet and has operated.The heat energy demand of implementing monomer droplet stabilization is very low.Due to these factors, the present invention is highly susceptible to implementing, and time implementation cycle of the present invention is shorter, and the present invention has cost benefit very much.
Equipment structure of the present invention very simply and easily operates.Equipment of the present invention only comprises a small amount of assembly, and very reliable.This equipment needs to safeguard hardly, and maintenance cost, fund cost and running cost aspect all have cost benefit.Equipment structure has further been simplified in the module structure of present device (wherein each several part can separately be produced or manufacture and assemble), and has shortened the assembly and disassembly time.
Because monomer droplet steadily and controllably upwards flows in reaction vessel, so the present invention has obtained following effect: avoided droplet coalescence and aggegation and broken, and having avoided having the thermal shocking of the polymer beads of the homogeneous particle diameter through improving.Therefore the ion exchange resin, being made by polymer beads of the present invention will have the kinetics of improvement in application.
Embodiment
Following examples are used for the present invention is described and do not limit its scope.
The mixture that use comprises 88.9 parts of vinylbenzene, 11.1 part of 63% Vinylstyrene and 37% ethyl styrene and based on monomer, be 0.67 part benzoyl peroxide monomer solution and comprise 0.3 part of polyvinyl alcohol and the aqueous solution of 4 parts of NaCl and excess water, in the exemplary apparatus of Fig. 1～3, test.In orifice plate, there are 25 apertures.Each aperture size is 0.2mm.In annulus, there are 20 holes.Each hole size is 1mm.Monomer solution is with flow velocity and the 0.3kg/cm of 2.7 ls/h
2pressure injection.Aqueous solution is with flow velocity and the 2.8kg/cm of 5 ls/h
2pressure injection.The aperture height of hole in annulus in orifice plate is that 25mm place separates.Volume ratio between monomer solution and aqueous solution is 1:4.Temperature in the monomer droplet stabilization portion of reaction vessel remains 55 ± 5 ℃.Polymer beads is 80 ± 5 ℃ of polymerizations.Wash polymer beads with water, at 90 ℃, be dried and sieve.The monomer of realizing to the transformation efficiency of polymkeric substance is greater than 95%, 80% particle diameter having within the scope of 0.4mm～0.5mm wherein, and there is 1.07 coefficient of uniformity.Polymer beads is functionalized to manufacture Zeo-karb.
Mixture and 38 parts of isopropylcarbinols that use comprises 55.6 parts of vinylbenzene, 6.4 part of 63% Vinylstyrene and 37% ethyl styrene and be the monomer solution of benzoyl peroxide of 0.8 part and the aqueous solution that comprises 0.3 part of Natvosol, 0.1Fen wooden sodium sulfonate, 15 parts of sodium-chlor and 2.5 parts of sodium-chlor based on monomer are tested in the exemplary apparatus of Fig. 1～3.In orifice plate, there are 25 apertures.Each aperture size is 0.2mm.In annulus, there are 20 holes.Each hole size is 1mm.Monomer solution is with flow velocity and the 0.3kg/cm of 6 ls/h
2pressure injection.Aqueous solution is with flow velocity and the 2.8kg/cm of 5 ls/h
2pressure injection.The aperture height of hole in annulus in orifice plate is that 25mm place separates.Volume ratio between monomer solution and aqueous solution is 1:4.Temperature in the monomer droplet stabilization portion of reaction vessel remains 55 ± 5 ℃.Pass through distillating recovering solvent.Polymer beads is 80 ± 5 ℃ of polymerizations.Wash polymer beads with water, at 90 ℃, be dried and sieve, to obtain bead, described bead has 75% particle diameter within the scope of 0.42mm～0.5mm, and has 1.1 coefficient of uniformity.Monomer to the transformation efficiency of polymkeric substance is greater than 95%.Polymer beads is functionalized to manufacture anionite-exchange resin.
Above embodiment shown in accompanying drawing of the present invention is used as embodiments of the invention, and should not be considered to and be interpreted as limit the scope of the invention.Can carry out some modification to the present invention, and not depart from its scope.Monomer solution dispenser and turbulent flow suppressing portion need not to be spherical.Pulsating monomer solution supply source and liquor supply source can have different formations or structure.Hyalomere can be made by any other transparent and mechanically resistant material.Monomer solution dispenser, monomer droplet stabilization portion and turbulent flow suppressing portion all can be made by any other corrosion resistant material.
Orifice plate and tubular ring can be made by any other corrosion resistant material.The lining of monomer droplet stabilization portion can be made by any other corrosion resistant material.Monomer solution tail pipe and valve are optional.Can be one-piece construction by device fabrication.If replace the monomer droplet stabilization portion with lining, this stabilization portion can be provided with other heating units, as an electric heating element.Bypass pipe and valve and liquor tail pipe and valve are all optional.Polymer reactor forms and structure can be different.To those skilled in the art, these modification of the present invention are apparent, and can be considered to and be interpreted as within the scope of the present invention.Scope of the present invention should be considered to and be interpreted as that the statement by following claim is limited and comprises in the inner.
Claims (15)
1. by suspension polymerization, prepare a method for the polymer beads of homogeneous particle diameter, described method comprises:
(i) at flow velocity and the 0.2Kg/cm of 2 ls/h～4 ls/h
2～1Kg/cm
2pressure under, with pulse mode, by being positioned at the monomer droplet of vertical setting, form a plurality of 50 microns～300 microns big or small apertures with reaction container bottom, the monomer solution of the polymerization single polymerization monomer that contains initiator is injected into the monomer liquid drip that makes progress mobile, and the while is at flow velocity and the 2.5Kg/cm of 4 ls/h～8 ls/h
2～3Kg/cm
2pressure under, with pulse mode by the hole of the periphery around described aperture and a plurality of 0.5mm～1mm sizes that are positioned at described reaction container bottom that separate above described aperture, to be injected in the same way the mobile fluid that makes progress with described monomer unmixing and the liquor that contains suspension stabilizer, volume ratio between described monomer solution and described liquor is 1:10, and described hole separates above described aperture with the distance of 10mm～40mm;
(ii) under the power applying at the density difference between the current difference between the pulsating supply source of monomer solution and liquor and pressure reduction and described monomer solution and described liquor, make monomer droplet in described liquor with controlled and stably mode in described reaction vessel, rise, and do not cause coalescent, the aggegation of described monomer droplet and break, and in described reaction vessel at 50 ℃～60 ℃, by the described suspension stabilizer in described liquor, by the partially polymerized monomer droplet stabilization that makes of described drop;
(iii) make the described monomer droplet in described liquor flatly flow into polymerization reactor from reaction vessel, and carrying out polymerization in 80 ℃～85 ℃ in described polymerization reactor, described polymerization reactor is equipped with agitator and is positioned at the position higher than described reaction vessel;
(iv) at 80 ℃～100 ℃ dry polymer beads; With
(v) sieve described polymer beads.
The method of claim 1, wherein described monomer solution be injected in flow velocity and the 0.3kg/cm of 2.7 ls/h～3.3 ls/h
2～0.5kg/cm
2pressure under by 150 microns～200 microns big or small apertures, undertaken, described liquor be injected in flow velocity and the 2.8kg/cm of 5 ls/h～6 ls/h
2pressure under hole by 0.8mm size carry out, the volume ratio between described monomer solution and liquor is 1:4, and described hole separates above described aperture with the distance of 25mm.
3. method as claimed in claim 1 or 2, wherein, described polymer beads is dry at 90 ℃.
4. by suspension polymerization, prepare an equipment for the polymer beads of homogeneous particle diameter, described equipment comprises:
The monomer droplet formation reaction vessel vertically arranging, described reaction vessel limits continuously and is positioned at the monomer solution dispenser of described reaction container bottom, the monomer droplet that is positioned at described monomer solution dispenser top and observes with the first hyalomere, the monomer droplet stabilization portion that is positioned at described the first hyalomere top, the monomer droplet that is positioned at described monomer droplet stabilization portion top and observe with the second hyalomere and be positioned at above described the second hyalomere and be positioned at turbulent flow inhibition and the drop discharge portion at described reaction vessel top
Wherein, described monomer solution dispenser its bottom be connected with pulsating monomer solution supply source, described monomer solution supply source can be at flow velocity and the 0.2Kg/cm of 2 ls/h～4 ls/h
2～1Kg/cm
2pressure under with pulse mode, supply with the monomer solution contain initiator, and described monomer solution dispenser comprises the injection orifice plate with a plurality of 50 microns～300 microns of big or small apertures at its top,
Described the first hyalomere comprises and is positioned at its bottom and above described orifice plate and the injection hollow tubular ring separating with distance and the described orifice plate of 10mm～40mm with respect to described orifice plate, described tubular ring around the described aperture periphery in described orifice plate and thereon surface there is the hole of a plurality of 0.5mm～1mm sizes that separate, described tubular ring is connected with pulsating liquor supply source, and described liquor supply source can be with flow velocity and the 2.5Kg/cm of 4 ls/h～8 ls/h
2～3Kg/cm
2pressure feed and described monomer solution unmixing the liquor that contains suspension stabilizer,
Volume ratio between described monomer solution and described liquor is 1:10, and
Described monomer droplet stabilization portion comprises heating unit, partly the described monomer droplet in described liquor is heated and stabilization in 50 ℃～60 ℃ in described monomer droplet stabilization portion, and
Described turbulent flow suppresses to comprise with drop discharge portion the monomer droplet outlet pipe being connected with polymerization reactor with horizontal droplet flow pipe, described polymer reactor is positioned near the position higher than described reaction vessel described horizontal droplet flow pipe, and its top is connected with described horizontal droplet flow pipe, described polymerization reactor is equipped with agitator and heating unit to heat and to make described monomer droplet aggregate into polymer beads at 80 ℃～85 ℃, and described polymerization reactor also has in its bottom the polymer beads delivery pipe that has been equipped with valve.
5. equipment as claimed in claim 4, wherein, described reaction vessel is module structure, described module structure comprises portion described in each removably fitting together.
6. the equipment as described in claim 4 or 5, wherein, described orifice plate comprises 150 microns～200 microns big or small apertures, and described pulsating monomer solution supply source is with flow velocity and the 0.3kg/cm of 2.7 ls/h～3.3 ls/h
2～0.5kg/cm
2pressure feed monomer solution, described tubular ring comprises the hole of 0.8mm size, and described pulsating liquid supply source is with flow velocity and the 2.8kg/cm of 5 ls/h～6 ls/h
2pressure feed liquor, the volume ratio between described monomer solution and liquor is 1:4, and the aperture in described orifice plate with the distance of 25mm of the hole in described tubular ring above separate.
7. the equipment as described in claim 4 or 5, wherein, described pulsating monomer solution supply source comprises tank, described tank has described monomer solution and is connected with described monomer solution dispenser by peristaltic pump, spinner-type flowmeter and pressure warning unit in its bottom.
8. the equipment as described in claim 4 or 5, wherein, described monomer solution dispenser is spherical form, and described monomer solution dispenser and orifice plate are made by stainless steel.
9. the equipment as described in claim 4 or 5, wherein, described pulsating liquor supply source comprises tank, described tank has described liquor and is connected with described tubular ring by peristaltic pump, spinner-type flowmeter and pressure warning unit.
10. the equipment as described in claim 4 or 5, wherein, described the first hyalomere is made by tempering transparent glass, and described tubular ring is made by stainless steel.
11. equipment as described in claim 4 or 5, wherein, described monomer droplet stabilization portion comprises lining, described lining has for hot-fluid entrance and hot-fluid that hot fluid circulation passes through are exported.
12. equipment as claimed in claim 11, wherein, described monomer droplet stabilization portion is made by stainless steel, and described lining is made by soft steel.
13. equipment as described in claim 4 or 5, wherein, described the second hyalomere is made by tempering transparent glass.
14. equipment as described in claim 4 or 5, wherein, described turbulent flow suppresses and drop discharge portion is spherical form, and is made by stainless steel.
15. equipment as described in claim 4 or 5, wherein, described polymerization reactor comprises lining and the polymer beads delivery pipe that is provided with valve that is positioned at described polymerization reactor bottom, and hot-fluid entrance and hot-fluid that described lining has for making hot fluid circulation pass through described lining export.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN2735MU2012 | 2012-09-20 | ||
| IN2735/MUM/2012 | 2012-09-20 |
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| CN103665232A true CN103665232A (en) | 2014-03-26 |
| CN103665232B CN103665232B (en) | 2016-08-24 |
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| CN201310426072.8A Active CN103665232B (en) | 2012-09-20 | 2013-09-18 | The method and apparatus being prepared the polymer beads of uniform particle size by suspension polymerisation |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US8816026B2 (en) |
| EP (1) | EP2711074B1 (en) |
| JP (1) | JP5749773B2 (en) |
| KR (1) | KR101658375B1 (en) |
| CN (1) | CN103665232B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924547A (en) * | 2016-07-07 | 2016-09-07 | 宁波争光树脂有限公司 | Spraying reaction device for suspension polymerization |
| CN108203514A (en) * | 2016-12-16 | 2018-06-26 | 漂莱特（中国）有限公司 | The method for producing uniform polymer beads by vibration jet using super-hydrophobic film |
| CN109569344A (en) * | 2018-12-17 | 2019-04-05 | 浙江大学 | A method of suspension microlayer model is prepared using micro fluidic device |
| CN109923131A (en) * | 2016-11-08 | 2019-06-21 | 陶氏环球技术有限责任公司 | Controlled size distribution |
| CN110128579A (en) * | 2019-04-13 | 2019-08-16 | 复旦大学 | High pass weight polymers library is automatically synthesized apparatus and method |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188368B (en) * | 2016-07-07 | 2018-08-24 | 宁波争光树脂有限公司 | A kind of preparation method of strong-base anion-exchange resin and products thereof and purposes |
| CN107715789B (en) * | 2017-10-23 | 2023-10-03 | 中国石油大学(北京) | Novel method and device for preparing polymer particles |
| US11548955B2 (en) * | 2017-11-10 | 2023-01-10 | DDP Specialty Electronic Materials US, Inc. | Component addition polymerization |
| CN111587225A (en) * | 2017-11-10 | 2020-08-25 | Ddp特种电子材料美国公司 | Component addition polymerization |
| CN107983281A (en) * | 2017-12-01 | 2018-05-04 | 成都欧林生物科技股份有限公司 | The regulating device of heating-up temperature in a kind of control reaction kettle |
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2013
- 2013-02-04 US US13/758,563 patent/US8816026B2/en active Active
- 2013-02-15 EP EP13155539.3A patent/EP2711074B1/en active Active
- 2013-09-16 KR KR1020130111342A patent/KR101658375B1/en active IP Right Grant
- 2013-09-18 CN CN201310426072.8A patent/CN103665232B/en active Active
- 2013-09-19 JP JP2013194450A patent/JP5749773B2/en active Active
-
2014
- 2014-07-21 US US14/336,757 patent/US9095832B2/en not_active Expired - Fee Related
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| US4444961A (en) * | 1980-10-30 | 1984-04-24 | The Dow Chemical Company | Process and apparatus for preparing uniform size polymer beads |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924547A (en) * | 2016-07-07 | 2016-09-07 | 宁波争光树脂有限公司 | Spraying reaction device for suspension polymerization |
| CN109923131A (en) * | 2016-11-08 | 2019-06-21 | 陶氏环球技术有限责任公司 | Controlled size distribution |
| CN109923131B (en) * | 2016-11-08 | 2021-10-26 | Ddp特种电子材料美国有限责任公司 | Controlled particle size distribution |
| CN108203514A (en) * | 2016-12-16 | 2018-06-26 | 漂莱特（中国）有限公司 | The method for producing uniform polymer beads by vibration jet using super-hydrophobic film |
| CN108203514B (en) * | 2016-12-16 | 2022-11-22 | 漂莱特（中国）有限公司 | Method for producing uniform polymer beads by vibro-jet using superhydrophobic membranes |
| CN109569344A (en) * | 2018-12-17 | 2019-04-05 | 浙江大学 | A method of suspension microlayer model is prepared using micro fluidic device |
| CN110128579A (en) * | 2019-04-13 | 2019-08-16 | 复旦大学 | High pass weight polymers library is automatically synthesized apparatus and method |
| CN110128579B (en) * | 2019-04-13 | 2021-08-20 | 复旦大学 | Automatic synthesis device and method for high-throughput polymer library |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103665232B (en) | 2016-08-24 |
| JP2014062252A (en) | 2014-04-10 |
| US20140080981A1 (en) | 2014-03-20 |
| US8816026B2 (en) | 2014-08-26 |
| US20140328722A1 (en) | 2014-11-06 |
| EP2711074B1 (en) | 2015-07-08 |
| KR101658375B1 (en) | 2016-09-21 |
| JP5749773B2 (en) | 2015-07-15 |
| EP2711074A1 (en) | 2014-03-26 |
| US9095832B2 (en) | 2015-08-04 |
| KR20140038326A (en) | 2014-03-28 |
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